CN108485599B - Preparation method of attapulgite-based broad-spectrum ultraviolet shielding material - Google Patents

Preparation method of attapulgite-based broad-spectrum ultraviolet shielding material Download PDF

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CN108485599B
CN108485599B CN201810244484.2A CN201810244484A CN108485599B CN 108485599 B CN108485599 B CN 108485599B CN 201810244484 A CN201810244484 A CN 201810244484A CN 108485599 B CN108485599 B CN 108485599B
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attapulgite
solution
shielding material
ultraviolet shielding
sodium
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CN108485599A (en
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姚超
王栋
左士祥
丁运生
朱俊武
刘文杰
李霞章
王灿
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Changzhou Nano Materials S&t Co ltd
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    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding

Abstract

The invention provides a preparation method of an attapulgite-based full-waveband ultraviolet shielding material, which takes attapulgite as a carrier and loads nano TiO on the carrier in situ2Then, the surface of the film is modified by aluminum, and DHHB is coated on TiO by a solvent evaporation method after the surface is modified by an anionic surfactant2The nano TiO is fully utilized on the ATP surface2The good shielding property of the medium-band ultraviolet rays and the good absorptivity of the DHHB to the long-band ultraviolet rays are compounded to prepare a brand-new broad-spectrum ultraviolet protective agent.

Description

Preparation method of attapulgite-based broad-spectrum ultraviolet shielding material
Technical Field
The invention belongs to the technical field of preparation of protective functional materials, and particularly relates to a preparation method of an attapulgite-based full-waveband ultraviolet shielding material.
Background
In the rays of solar radiation, there are approximately 5% of ultraviolet rays having a wavelength of 400nm or less. Ultraviolet rays in sunlight are classified into: wavelength of 32Long-wave ultraviolet rays of 0 to 400nm, called type A ultraviolet rays (UVA); medium-wave ultraviolet rays having a wavelength of 280 to 320nm, called B-type ultraviolet rays (UVB), and short-wave ultraviolet rays having a wavelength of 200 to 280nm, called C-type ultraviolet rays (UVC). UVC is basically absorbed when passing through the ozone layer, and cannot cause damage to terrestrial organisms. Research shows that UVB can cause skin inflammation and sunburn; UVA is the major cause of tanning and the induction of skin cancer. Because of rutile type nano TiO2High screening efficiency to UVB, safety, innocuity, good chemical stability and light stability, and the like, and is widely applied to the field of sunscreen cosmetics. Because of the nano TiO2The particle has large specific surface area and high surface energy, is easy to initiate agglomeration, influences the ultraviolet shielding performance of the particle, and overcomes the defects of the nano TiO2The spontaneous agglomeration of particles and the maintenance of the excellent UVB shielding effect are always the research direction.
Rutile type nano TiO2Although UVB can be efficiently shielded, the shielding effect on UVA is poor, and it is necessary to compound it in order to achieve broad-spectrum uv protection. The organic ultraviolet absorbent has the advantages of rich varieties, strong ultraviolet absorption capability, easy formulation and the like. The Diethylamino Hydroxybenzoyl Hexyl Benzoate (DHHB) serving as a novel organic ultraviolet absorbent has an excellent absorption effect on long-wave-band Ultraviolet (UVA) and good stability, so that the Diethylamino Hydroxybenzoyl Hexyl Benzoate (DHHB) has good application potential.
Attapulgite (ATP), also known as palygorskite, is a magnesium-aluminum-rich silicate clay mineral with a nano rod-shaped structure, and has excellent adsorption performance, colloidal property and salt resistance. Attapulgite is used as a unique nonmetallic mineral resource in China, is mainly concentrated in Suwan regions, has the advantages of rich reserves, low price, chemical inertness and the like, and has been used as a carrier material in many fields for reducing the agglomeration of active components.
Disclosure of Invention
Aiming at the problems in the background art, the invention aims to provide a preparation method of an attapulgite-based broad-spectrum ultraviolet shielding material.
The preparation method of the attapulgite-based broad-spectrum ultraviolet shielding material comprises the following steps:
(1)adding a titanium tetrachloride solution with a molar concentration of 1.0-4.0 mol/l into a sodium hydroxide solution with a molar concentration of 1.0-4.0 mol/l while stirring at a temperature of 50-60 ℃, keeping the temperature for curing for 0.5-1.5 hours, then adding an attapulgite slurry with a solid content of 20-80 g/l while stirring, and keeping the temperature for curing for 1.5-3 hours. Adding a soluble aluminum salt solution having a molar concentration of 1.0 to 4.0 mol/l, adjusting the pH of the system to 9.0 to 10.0 using an alkaline solution having a molar concentration of 0.5 to 2.0 mol/l, and aging for 0.5 to 1.5 hours. Adjusting the pH value of the system to be 4.0-5.0 by using an acid solution with the molar concentration of 0.5-2.0 mol/L, adding a certain amount of anionic surfactant, and preserving heat for curing for 1.5-3.0 hours. Filtering, washing, drying at 80-110 deg.C, and pulverizing to obtain attapulgite-based broad-spectrum ultraviolet shielding material (organic surface modified nanometer TiO)2a/ATP complex);
in the step (1), the mass ratio of the titanium tetrachloride solution to the sodium hydroxide solution is 0.8-1.2: 2, the mass ratio of the titanium tetrachloride to the attapulgite is 1-1.5: 1, the soluble aluminum salt is sodium metaaluminate, aluminum chloride, aluminum sulfate or aluminum nitrate, the mass ratio of the soluble aluminum salt to the attapulgite is 0.1-0.3: 1, the alkaline solution is sodium hydroxide, ammonia water, sodium carbonate or sodium bicarbonate, the mass ratio of the alkaline solution to the attapulgite is 0.02-0.2: 1, and the acidic solution is: hydrochloric acid, sulfuric acid or nitric acid, and attapulgite according to the mass ratio of 0.1-0.2: 1; the anionic surfactant is sodium laurate, sodium stearate, sodium secondary alkyl sulfonate or sodium dodecyl benzene sulfonate, and the mass ratio of the anionic surfactant to the attapulgite is 0.1-0.3: 1,
(2) modifying the organic surface modified nano TiO prepared in the step (1)2The ATP composite material is uniformly dispersed into dichloromethane to prepare nano TiO with the solid content of 100-400 g/L2The ATP composite material is prepared by adding 200-400 g/L diethyl-amino-hydroxybenzoyl-hexyl benzoate (DHHB) dichloromethane solution while stirring at 30-40 ℃, heating to 45-50 ℃, condensing and recycling dichloromethane until all solvents are removed, and the nano TiO is prepared2the/ATP @ DHHB composite material.
Wherein the ratio of the DHHB dosage to the mass of the organic surface modified attapulgite is 0.2-0.4: 1, and the temperature rise range is 40-45 ℃.
The invention has the beneficial effects that:
1. the invention fully utilizes the one-dimensional nano-fiber structure characteristic of attapulgite, takes the attapulgite as a carrier, and utilizes the surface hydroxyl of the attapulgite to load nano TiO on the carrier in situ2To reduce the agglomeration, enhance the dispersibility and improve the nano TiO2Shielding performance of middle wave band ultraviolet ray and improving nano TiO by aluminium inorganic modification2The light stability of (1). Because the coating process of the DHHB is carried out in an oil phase system dichloromethane, the DHHB is subjected to surface modification by using an anionic modifier ionic surfactant to improve the dispersibility, which is beneficial to improving the uniformity of the DHHB coating, controlling the self-phase crystallization of the DHHB and controlling the particle size of the DHHB.
2. The invention coats DHHB on TiO by a solvent evaporation method2The nano TiO is fully utilized on the ATP surface2The good shielding property of the medium-band ultraviolet rays and the good absorptivity of the DHHB to the long-band ultraviolet rays are compounded to prepare a brand-new broad-spectrum ultraviolet protective agent. Meanwhile, the prepared sample is oleophilic and hydrophobic, and has good ultraviolet shielding effect when being used in the fields of high polymer materials such as rubber, plastics, coatings and the like, and the attapulgite fiber is used as a reinforcing agent and can improve the mechanical property of the high polymer materials; it is used in cosmetic field, and has effects of shielding ultraviolet ray, and moisturizing attapulgite as nucleus body containing large amount of crystal water.
Drawings
FIG. 1 is a graph showing sunscreen properties of emulsions prepared using UV-screening material powders according to examples of the present invention and comparative examples.
Detailed Description
Example 1
1. 1.0 liter of a titanium tetrachloride solution having a molarity of 2.0 mols/liter was added to 2.0 liters of oxyhydrogen having a molarity of 2.5 mols/liter under stirring at a temperature of 50 deg.CAnd (3) after the sodium chloride solution is subjected to heat preservation and aging for 0.5 hour, adding 30 liters of attapulgite slurry with the solid content of 40 g/liter while stirring, and carrying out heat preservation and aging for 2.5 hours. 0.2 liter of a sodium metaaluminate solution having a molarity of 1.5 mol/liter was added, the system pH was adjusted to 9.0 to 10.0 using 0.1 liter of a sodium hydroxide solution having a molarity of 1.0 mol/liter, and aging was carried out for 1 hour. Adjusting the pH of the system to 4.0-5.0 by using 0.2L nitric acid solution with the molar concentration of 0.8 mol/L, adding 0.2 kg sodium dodecyl benzene sulfonate, and preserving heat for curing for 2.0 hours. Filtering, washing, drying at 110 deg.C, and pulverizing to obtain organic surface modified nanometer TiO2a/ATP composite.
2. Modifying the organic surface modified nano TiO prepared in the step 12The ATP composite material is evenly dispersed into dichloromethane to prepare nano TiO with the solid content of 200 g/L2The ATP composite material is prepared by adding 500 liters of DHHB dichloromethane solution with the mass concentration of 300 g/liter under the condition of stirring at the temperature of 40 ℃, heating to 45 ℃, condensing and recycling dichloromethane until all solvents are removed, and then the nano TiO is prepared2the/ATP @ DHHB composite material.
Example 2
1. 2.0 liters of titanium tetrachloride solution having a molar concentration of 3.0 moles/liter was added to 4.5 liters of sodium hydroxide solution having a molar concentration of 2.0 moles/liter at a temperature of 57 ℃ while stirring, and after 1.2 hours of aging under heat preservation, 50 liters of attapulgite slurry having a solid content of 50 g/liter was added while stirring, and after 2 hours of aging under heat preservation. 0.15 liter of an aluminum sulfate solution having a molarity of 2.0 mols/liter was added, the system pH was adjusted to 9.0 to 10.0 using 0.2 liter of a sodium carbonate solution having a molarity of 0.5 mols/liter, and aging was carried out for 1.2 hours. Adjusting pH of the system to 4.0-5.0 with 0.3L hydrochloric acid solution with 1.0 mol/L, adding 0.3 kg sodium laurate, and aging for 1.5 hr under heat preservation. Filtering, washing, drying at 80 deg.C, and pulverizing to obtain organic surface modified nanometer TiO2An ATP-complex;
2. modifying the organic surface modified nano TiO prepared in the step 12The ATP composite material is uniformly dispersed into dichloromethane, and the prepared solid content is 300 g/l nano TiO2The ATP composite material is prepared by adding 600 liters of DHHB dichloromethane solution with the mass concentration of 350 g/liter under the condition of stirring at the temperature of 35 ℃, heating to 50 ℃, condensing and recycling dichloromethane until all solvents are removed, and then the nano TiO is prepared2the/ATP @ DHHB composite material.
Example 3
1. 3.0 liters of titanium tetrachloride solution having a molar concentration of 3.5 mol/liter was added to 5.0 liters of sodium hydroxide solution having a molar concentration of 4.0 mol/liter at a temperature of 54 ℃ while stirring, and after 1 hour of aging under holding temperature, 100 liters of attapulgite slurry having a solid content of 75 g/liter was added while stirring, and then aged under holding temperature for 3 hours. 0.05 liter of an aluminum chloride solution having a molarity of 3.0 mols/liter was added, the system pH was adjusted to 9.0 to 10.0 using 0.15 liter of an aqueous ammonia solution having a molarity of 1.5 mols/liter, and aging was carried out for 0.8 hour. The pH of the system was adjusted to 4.0 to 5.0 using 0.3 l hydrochloric acid solution of 2.0 mol/l, and 0.25 kg of sodium stearate was added thereto, followed by aging for 2.5 hours under constant temperature. Filtering, washing, drying at 100 deg.C, and pulverizing to obtain organic surface modified nanometer TiO2An ATP-complex;
2. modifying the organic surface modified nano TiO prepared in the step 12The ATP composite material is evenly dispersed into dichloromethane to prepare nano TiO with the solid content of 250 g/L2The ATP composite material is prepared by adding 750 liters of dichloromethane solution of DHHB with the mass concentration of 400 g/liter into the ATP composite material under the condition of stirring at the temperature of 30 ℃, heating to 48 ℃, condensing and recycling dichloromethane until all solvents are removed, and then the nano TiO is prepared2the/ATP @ DHHB composite material.
Example 4
1. 4.0 liters of titanium tetrachloride solution with a molar concentration of 1.0 mol/liter was added to 4.5 liters of sodium hydroxide solution with a molar concentration of 2.0 mol/liter at a temperature of 60 ℃ while stirring, and after 1.5 hours of aging under heat preservation, 60 liters of attapulgite slurry with a solid content of 50 g/liter was added while stirring, and after 1.5 hours of aging under heat preservation. 0.1 liter of an aluminum nitrate solution having a molarity of 3.0 mols/liter was added, and 0.1 liter of an aluminum nitrate solution having a molarity of 2.0 mols/liter was usedThe pH of the system was adjusted to 9.0 to 10.0 with sodium bicarbonate solution, and the mixture was aged for 1.5 hours. Adjusting pH of the system to 4.0-5.0 with 0.2L sulfuric acid solution with 0.8 mol/L, adding 0.2 g secondary alkyl sodium sulfonate, and aging for 3.0 hr. Filtering, washing, drying at 90 deg.C, and pulverizing to obtain organic surface modified nanometer TiO2An ATP-complex;
2. modifying the organic surface modified nano TiO prepared in the step 12The ATP composite material is evenly dispersed into dichloromethane to prepare nano TiO with the solid content of 400 g/L2The ATP composite material is prepared by adding 550 liters of DHHB dichloromethane solution with the mass concentration of 200 g/liter under the condition of stirring at the temperature of 40 ℃, heating to 45 ℃, condensing and recycling dichloromethane until all solvents are removed, and then the nano TiO is prepared2the/ATP @ DHHB composite material.
Comparative example 1
In comparative example 1, the procedure of coating DHHB in example 4 was removed, and the other procedures were the same as in example 4;
comparative example 2
In comparative example 2, the attapulgite in example 4 was removed, and the other operation steps were the same as in example 4;
comparative example 3
In comparative example 3, the nano TiO of example 4 was used2Removing, and other operation steps are the same as example 4;
comparative example 4
In comparative example 4, the organic modification step in example 4 was removed, and the remaining operation steps were the same as in example 4, and the specific operation was as follows:
1. 4.0 liters of titanium tetrachloride solution with a molar concentration of 1.0 mol/liter was added to 4.5 liters of sodium hydroxide solution with a molar concentration of 2.0 mol/liter at a temperature of 60 ℃ while stirring, and after 1.5 hours of aging under heat preservation, 60 liters of attapulgite slurry with a solid content of 50 g/liter was added while stirring, and after 1.5 hours of aging under heat preservation. 0.1 liter of an aluminum nitrate solution having a molarity of 3.0 mols/liter was added thereto, and 0.1 liter of a sodium hydrogencarbonate solution having a molarity of 2.0 mols/liter was used to adjust the pH of the system to 9.0 to 10.0,and aged for 1.5 hours. The pH of the system was adjusted to 4.0 to 5.0 using 0.2 l of a 0.8 mol/l sulfuric acid solution. Filtering, washing, drying at 90 deg.C, and pulverizing to obtain organic surface modified nanometer TiO2An ATP-complex;
2. modifying the organic surface modified nano TiO prepared in the step 12The ATP composite material is evenly dispersed into dichloromethane to prepare nano TiO with the solid content of 400 g/L2The ATP composite material is prepared by adding 550 liters of DHHB dichloromethane solution with the mass concentration of 200 g/liter under the condition of stirring at the temperature of 40 ℃, heating to 45 ℃, condensing and recycling dichloromethane until all solvents are removed, and then the nano TiO is prepared2the/ATP @ DHHB composite material.
The composite materials prepared in examples and comparative examples were added to ethanol to prepare 20ppm dispersions, and after further ultrasonic dispersion for 30 minutes, the absorbances of light were measured on an ultraviolet-visible near infrared spectrophotometer (UV3600, shimadzu corporation, japan) using a quartz cuvette of the optical path 1Cm and ethanol removal as a reference, respectively. Absorbance at 308nm is represented by A308The reaction is the shielding capability of the composite powder to UVB, A308The larger the shielding capacity, the better the shielding capacity of UVB; absorbance at 360nm is represented by A360The reaction is the shielding capability of the composite powder to UVA, A360The larger the signal, the better the UVA shielding ability. The experimental results are shown in table 1. As can be seen from the table, the attapulgite-based ultraviolet shielding composite material prepared by the invention has excellent full-wave band ultraviolet shielding effect and strong shielding capability on UVA and UVB.
TABLE 1 Absorbance test results for different materials
Figure BDA0001606151180000071
Figure BDA0001606151180000081
The ultraviolet shielding material powder prepared by each example and comparative example of the present invention was applied to the formulationThe emulsion (the formula of the emulsion is shown in Table 2) is used for measuring the ultraviolet protection effect of the sample in practical application. When the powder addition amount is 10%, the sunscreen performance curve of the emulsion prepared by different powders is shown in the figure 1, and the sunscreen index is shown in the table 3. As can be seen, examples 1-4 all provided effective protection in the range of 290-380nm, while comparative examples all had poor UV protection. It can be seen from table 3 that examples 1-4 show more excellent SPF and UVA values than comparative examples 1-4 in the emulsion formulation. Meanwhile, the critical wavelength (lambada c) of the sample is always larger than 380nm, which can show that the nano TiO is2the/ATP @ DHHB composite material has a good broad-spectrum ultraviolet protection effect.
TABLE 2
Figure BDA0001606151180000082
TABLE 3 Sun protection index of different powders
Sample (I) SPA PFA λc(nm)
Example 1 12.03 11.56(+++) 381
Example 2 12.10 11.64(+++) 381
Example 3 11.96 11.46(+++) 383
Example 4 12.18 11.37(+++) 381
Comparative example 1 8.01 2.13(+) 372
Comparative example 2 5.98 5.67(++) 374
Comparative example 3 2.04 9.63(++) 375
Comparative example 4 6.52 5.91(++) 375

Claims (7)

1. A preparation method of an attapulgite-based broad-spectrum ultraviolet shielding material is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) adding titanium tetrachloride solution into the mixture under stirring at the temperature of 50-60 DEG CAdding the attapulgite slurry into a sodium hydroxide solution, preserving heat and curing for 0.5 to 1.5 hours, adding the attapulgite slurry under the stirring condition, and preserving heat and curing for 1.5 to 3 hours; adding a soluble aluminum salt solution, adjusting the pH value of the system to 9.0-10.0 by using an alkaline solution, and curing for 0.5-1.5 hours; adjusting the pH value of the system to 4.0-5.0 by using an acid solution, adding an anionic surfactant, preserving heat, curing for 1.5-3.0 hours, performing suction filtration, washing, drying at the temperature of 80-110 ℃, and crushing to obtain the organic surface modified nano TiO2An ATP-complex;
(2) modifying the organic surface modified nano TiO prepared in the step (1)2The ATP composite material is uniformly dispersed into dichloromethane to prepare nano TiO with the solid content of 100-400 g/L2The ATP composite material is prepared by adding a dichloromethane solution of diethyl-amino-hydroxybenzoyl hexyl benzoate DHHB under the stirring condition at the temperature of 30-40 ℃, heating to 45-50 ℃, condensing and recycling dichloromethane until all solvents are removed, and thus obtaining the attapulgite-based broad-spectrum ultraviolet shielding material;
the mass concentration of the dichloromethane solution of the diethyl hydroxyl benzoyl hexyl benzoate is 200-400 g/L, the mass ratio of the diethyl hydroxyl benzoyl hexyl benzoate to the organic surface modified attapulgite is 0.2-0.4: 1, and the temperature is increased by 40-45 ℃.
2. The method for preparing the attapulgite-based broad spectrum ultraviolet shielding material according to claim 1, wherein the method comprises the following steps: the molar concentration of the titanium tetrachloride solution in the step (1) is 1.0-4.0 mol/L; the molar concentration of the sodium hydroxide solution is 1.0-4.0 mol/L; the solid content of the attapulgite slurry is 20-80 g/L.
3. The method for preparing the attapulgite-based broad spectrum ultraviolet shielding material according to claim 1, wherein the method comprises the following steps: the molar concentration of the soluble aluminum salt solution in the step (1) is 1.0-4.0 mol/L; the molar concentration of the alkaline solution is 0.5-2.0 mol/L; the molar concentration of the acidic solution is 0.5-2.0 mol/L.
4. The method for preparing the attapulgite-based broad spectrum ultraviolet shielding material according to claim 1, wherein the method comprises the following steps: the mass ratio of the titanium tetrachloride solution to the sodium hydroxide solution in the step (1) is 0.8-1.2: 2, and the mass ratio of the titanium tetrachloride to the attapulgite is 1-1.5: 1.
5. The method for preparing the attapulgite-based broad spectrum ultraviolet shielding material according to claim 1, wherein the method comprises the following steps: the soluble aluminum salt in the step (1) is sodium metaaluminate, aluminum chloride, aluminum sulfate or aluminum nitrate, and the mass ratio of the soluble aluminum salt to the attapulgite is 0.1-0.3: 1.
6. The method for preparing the attapulgite-based broad spectrum ultraviolet shielding material according to claim 1, wherein the method comprises the following steps: the alkaline solution in the step (1) is sodium hydroxide, ammonia water, sodium carbonate or sodium bicarbonate, the mass ratio of the alkaline solution to the attapulgite is 0.02-0.2: 1, and the acidic solution is as follows: the mass ratio of the hydrochloric acid, the sulfuric acid or the nitric acid to the attapulgite is 0.1-0.2: 1.
7. The method for preparing the attapulgite-based broad spectrum ultraviolet shielding material according to claim 1, wherein the method comprises the following steps: the anionic surfactant in the step (1) is sodium laurate, sodium stearate, sodium secondary alkyl sulfonate or sodium dodecyl benzene sulfonate, and the mass ratio of the anionic surfactant to the attapulgite is 0.1-0.3: 1.
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